JPH09249627A - Method for stabilizing N-vinylcarboxylic acid amide - Google Patents
Method for stabilizing N-vinylcarboxylic acid amideInfo
- Publication number
- JPH09249627A JPH09249627A JP8052965A JP5296596A JPH09249627A JP H09249627 A JPH09249627 A JP H09249627A JP 8052965 A JP8052965 A JP 8052965A JP 5296596 A JP5296596 A JP 5296596A JP H09249627 A JPH09249627 A JP H09249627A
- Authority
- JP
- Japan
- Prior art keywords
- acid amide
- group
- vinylcarboxylic acid
- formula
- stabilizing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 21
- 230000000087 stabilizing effect Effects 0.000 title claims abstract description 13
- 150000001728 carbonyl compounds Chemical class 0.000 claims abstract description 14
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 13
- 125000003118 aryl group Chemical group 0.000 claims abstract description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 9
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 8
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 11
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 claims description 6
- AXMVYSVVTMKQSL-UHFFFAOYSA-N UNPD142122 Natural products OC1=CC=C(C=CC=O)C=C1O AXMVYSVVTMKQSL-UHFFFAOYSA-N 0.000 claims description 6
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 claims description 6
- 229940117916 cinnamic aldehyde Drugs 0.000 claims description 6
- 239000001211 (E)-4-phenylbut-3-en-2-one Substances 0.000 claims description 3
- BATOPAZDIZEVQF-MQQKCMAXSA-N (E,E)-2,4-hexadienal Chemical compound C\C=C\C=C\C=O BATOPAZDIZEVQF-MQQKCMAXSA-N 0.000 claims description 3
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 claims description 3
- 229930008407 benzylideneacetone Natural products 0.000 claims description 3
- 229930016911 cinnamic acid Natural products 0.000 claims description 3
- 235000013985 cinnamic acid Nutrition 0.000 claims description 3
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 claims description 3
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 claims description 3
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 claims description 3
- BATOPAZDIZEVQF-UHFFFAOYSA-N sorbic aldehyde Natural products CC=CC=CC=O BATOPAZDIZEVQF-UHFFFAOYSA-N 0.000 claims description 3
- BWHOZHOGCMHOBV-BQYQJAHWSA-N trans-benzylideneacetone Chemical compound CC(=O)\C=C\C1=CC=CC=C1 BWHOZHOGCMHOBV-BQYQJAHWSA-N 0.000 claims description 3
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 3
- 230000006641 stabilisation Effects 0.000 claims 1
- 238000011105 stabilization Methods 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 6
- 238000000746 purification Methods 0.000 abstract description 5
- 229920000642 polymer Polymers 0.000 description 13
- 239000003381 stabilizer Substances 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 10
- 238000004821 distillation Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000012856 packing Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 3
- 150000004982 aromatic amines Chemical class 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000000539 dimer Substances 0.000 description 3
- -1 formylalanine nitrile Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000012719 thermal polymerization Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- OBSOFSUMTBYDCT-UHFFFAOYSA-N n-(1-methoxyethyl)formamide Chemical compound COC(C)NC=O OBSOFSUMTBYDCT-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2 ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000004181 carboxyalkyl group Chemical group 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- SJSZBOAQWPKFMU-UHFFFAOYSA-N n-(1-acetamidoethyl)acetamide Chemical compound CC(=O)NC(C)NC(C)=O SJSZBOAQWPKFMU-UHFFFAOYSA-N 0.000 description 1
- NBNDPGGJEJRDBJ-UHFFFAOYSA-N n-(2-formamidoethyl)formamide Chemical compound O=CNCCNC=O NBNDPGGJEJRDBJ-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000005935 nucleophilic addition reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical group O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
(57)【要約】
【課題】 Ｎ−ビニルカルボン酸アミドの精製、貯蔵、
移動時における安定性を高める。
【解決手段】 Ｎ−ビニルカルボン酸アミドに、下記の
式（１）で表されるα，β−不飽和カルボニル化合物を
添加することを特徴とするＮ−ビニルカルボン酸アミド
の安定化方法。
【化１】
（式（１）において、Ｒ1は水素原子、アルキル基、ア
リール基又はアルコキシ基、Ｒ2はアルキル基、アルケ
ニル基又はアリール基、Ｒ3，Ｒ4は水素原子、アルキル
基、アルケニル基又はアリール基を表す。）(57) Abstract: Purification and storage of N-vinylcarboxylic acid amide,
Improves stability when moving. A method for stabilizing an N-vinylcarboxylic acid amide, which comprises adding an α, β-unsaturated carbonyl compound represented by the following formula (1) to the N-vinylcarboxylic acid amide. Embedded image (In the formula (1), R 1 is a hydrogen atom, an alkyl group, an aryl group or an alkoxy group, R 2 is an alkyl group, an alkenyl group or an aryl group, and R 3 and R 4 are a hydrogen atom, an alkyl group, an alkenyl group or an aryl group. Represents a group.)
Description
【０００１】[0001]
【発明の属する技術分野】本発明はＮ−ビニルカルボン
酸アミドの安定化方法に関する。さらに詳しくは、N-ビ
ニルカルボン酸アミドの精製、移動、貯蔵などの取り扱
いにおいて、Ｎ−ビニルカルボン酸アミドの損失を防止
する方法に関する。TECHNICAL FIELD The present invention relates to a method for stabilizing N-vinylcarboxylic acid amide. More specifically, it relates to a method for preventing loss of N-vinylcarboxylic acid amide in handling such as purification, transfer and storage of N-vinylcarboxylic acid amide.
【０００２】[0002]
【従来の技術】Ｎ−ビニルカルボン酸アミドは、一般式2. Description of the Related Art N-vinyl carboxylic acid amides have the general formula
【０００３】[0003]
【化３】ＣＨ2 ＝ＣＨＮＨＣＯＲ （式中、Ｒは水素原子またはアルキル基を表す。）で示
され、Ｎ−ビニルアミドあるいはＮ−ビニルアシルアミ
ドとも呼ばれている重合性に富む化合物であり、単独で
重合させるか又は他のビニル化合物と共重合させて、種
々の特性を有する重合物を得ることができる。この重合
物を加水分解してそのアミド基を１級アミノ基に転換し
て得られるポリビニルアミン等の水溶性ポリマーの原
料、あるいは有機薬品の中間体として有用であることが
知られている。Embedded image CH 2 ═CHNHCOR (wherein R represents a hydrogen atom or an alkyl group), which is a compound having high polymerizability and is also called N-vinylamide or N-vinylacylamide. Can be polymerized with or copolymerized with other vinyl compounds to obtain polymers having various properties. It is known that this polymer is hydrolyzed to convert its amide group into a primary amino group, and is useful as a raw material of a water-soluble polymer such as polyvinylamine or an intermediate of an organic chemical.
【０００４】このＮ−ビニルカルボン酸アミドは反応性
に富む物質であり、容易に分解または重合し、損失され
る。また、加熱により熱重合せしめたときの重合体は、
多くの場合不溶不融の架橋物を与え、装置の閉塞などを
引き起こす。このため、製造工程ならびに貯蔵の際の安
定化法として、種々の方法が提案されているが、Ｎ−ビ
ニルアミドに安定化剤を添加する方法が最も一般的であ
る。This N-vinylcarboxylic acid amide is a highly reactive substance, which easily decomposes or polymerizes and is lost. Further, the polymer when heat-polymerized by heating,
In many cases, an insoluble and infusible crosslinked product is given, which causes blockage of the device. For this reason, various methods have been proposed as a stabilizing method during the manufacturing process and during storage, but the method of adding a stabilizer to N-vinylamide is the most general method.
【０００５】安定化剤としては、ラジカル重合禁止剤と
しての性質を有する置換フェノール類、芳香族アミン
類、ハイドロキノン類等の使用が提案されている（特開
昭６１−２３６７５７、特開平２ー２７０８４６、特開
平６ー１２２６６０等）。また、特開平６ー４１０３４
号公報には、Ｎ−ビニルカルボン酸アミドの安定化に効
果のあるビニル化合物として酢酸ビニル、アクリロニト
リル、Ｎ−ビニルピロリドン等が例示されている。As stabilizers, use of substituted phenols, aromatic amines, hydroquinones and the like having properties as radical polymerization inhibitors has been proposed (JP-A-61-236757, JP-A-2-270846). , JP-A-6-122660). In addition, JP-A-6-41034
In the publication, vinyl acetate, acrylonitrile, N-vinylpyrrolidone and the like are exemplified as vinyl compounds effective for stabilizing N-vinylcarboxylic acid amide.
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、置換フ
ェノール類、芳香族アミン類、ハイドロキノン類等の安
定化剤においては、蒸留時における熱重合の防止に使用
する際、Ｎ−ビニルカルボン酸アミドとともに溜出して
しまったり、蒸留塔内での均一な分布を達成することが
困難であるなどにより、効果が不十分であるという問題
がある。また、これらの化合物は、毒性が強かったり、
着色している場合が多く、移動または貯蔵の際の安定化
剤として用いた場合に、製品の品質を損なうことがあ
る。However, stabilizers such as substituted phenols, aromatic amines, and hydroquinones are used together with N-vinylcarboxylic acid amide when they are used to prevent thermal polymerization during distillation. There is a problem that the effect is insufficient due to the fact that it is taken out or it is difficult to achieve a uniform distribution in the distillation column. In addition, these compounds are highly toxic,
They are often colored and may impair the quality of the product when used as stabilizers during transport or storage.
【０００７】一方、前記の特開平６ー４１０３４号公報
で示されている化合物を用いて有効な安定化効果を得る
ためには、Ｎ−ビニルカルボン酸アミドと同量前後とい
った大量の添加量を必要とし、高純度のＮ−ビニルカル
ボン酸アミドを得るためには再度の精製が不可欠であ
り、実用的とは言いがたい。On the other hand, in order to obtain an effective stabilizing effect by using the compound disclosed in the above-mentioned JP-A-6-41034, a large addition amount such as about the same amount as N-vinylcarboxylic acid amide is used. Repurification is indispensable in order to obtain N-vinylcarboxylic acid amide with high purity, which is not practical.
【０００８】[0008]
【課題を解決するための手段】本発明者等は、以上の問
題点に鑑み、Ｎ−ビニルカルボン酸アミドの精製、移
動、貯蔵などの取り扱いにおいて、分解または重合によ
る損失の抑制に有効なＮ−ビニルカルボン酸アミドの新
規安定化方法について鋭意検討を行った結果、β位に少
なくとも一つ置換基を持つような特定α，β−不飽和カ
ルボニル化合物が、Ｎ−ビニルカルボン酸アミドの安定
化に顕著な効果があることを見出し、本発明に到達し
た。In view of the above problems, the present inventors have found that N-vinylcarboxylic acid amide is effective in suppressing loss due to decomposition or polymerization in handling such as purification, transfer and storage. -As a result of extensive studies on a novel method for stabilizing vinylcarboxylic acid amide, a specific α, β-unsaturated carbonyl compound having at least one substituent at the β-position stabilizes N-vinylcarboxylic acid amide. The present invention has been accomplished by finding that there is a remarkable effect on
【０００９】即ち、本発明は、Ｎ−ビニルカルボン酸ア
ミドに、下記の式（１）又は（２）で表されるα，β−
不飽和カルボニル化合物を添加することを特徴とするＮ
−ビニルアミドの安定化方法に存する。That is, the present invention provides N-vinylcarboxylic acid amides with α, β-represented by the following formula (1) or (2).
N characterized by adding an unsaturated carbonyl compound
-A method of stabilizing vinylamide.
【００１０】[0010]
【化４】 （式（１）において、Ｒ1は水素原子、アルキル基、ア
リール基又はアルコキシ基、Ｒ2はアルキル基、アルケ
ニル基又はアリール基、Ｒ3，Ｒ4は水素原子、アルキル
基、アルケニル基又はアリール基を表す。）Embedded image (In the formula (1), R 1 is a hydrogen atom, an alkyl group, an aryl group or an alkoxy group, R 2 is an alkyl group, an alkenyl group or an aryl group, and R 3 and R 4 are a hydrogen atom, an alkyl group, an alkenyl group or an aryl group. Represents a group.)
【００１１】[0011]
【発明の実施の形態】以下、本発明について詳細に説明
する。本発明で安定化の対象となるＮ−ビニルカルボン
酸アミドの製造方法は特に限定されない。その製造方法
としては、Ｎ−（α−アルコキシエチル）ホルムアミド
からアルコールを脱離させる方法（米国特許明細書３，
９１４，３０４号）、ホルミルアラニンニトリルからシ
アン化水素を脱離させる方法（特開昭６１−１３４３５
９）、及び、エチレンビスホルムアミドあるいはエチリ
デンビスアセトアミドを熱分解する方法（米国特許第
４，０１８，８２６号、同４，４９０，５５７号、同
４，５７８，５１５号）などがある。これらの方法は、
いずれも、減圧下、１００℃以上の高温で熱分解して、
Ｎ−ビニルカルボン酸アミドを得るものである。Ｎ−ビ
ニルカルボン酸アミドは、通常、該熱分解混合液より蒸
留により、通常８０重量％以上の純度の粗Ｎ−ビニルカ
ルボン酸アミドが回収される。また、本発明で安定化の
対象となるＮ−ビニルカルボン酸アミドは以上のような
粗製品でもよいし、精製品であってもよい。即ち、本発
明で用いる安定剤は、Ｎ−ビニルカルボン酸アミドの製
造工程において、熱分解工程から得られた蒸留精製前の
Ｎ−ビニルカルボン酸アミドに添加して、該安定剤の存
在下で蒸留することにより、その蒸留工程における安定
化を図ることができる。また、精製されたＮ−ビニルカ
ルボン酸アミドに添加して組成物の状態で保管及び輸送
し、その際の安定性を高めることができる。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The method for producing the N-vinylcarboxylic acid amide to be stabilized in the present invention is not particularly limited. As its production method, a method of desorbing alcohol from N- (α-alkoxyethyl) formamide (US Pat.
914, 304), and a method for desorbing hydrogen cyanide from formylalanine nitrile (JP-A-61-143535).
9) and a method of thermally decomposing ethylenebisformamide or ethylidenebisacetamide (US Pat. Nos. 4,018,826, 4,490,557 and 4,578,515). These methods are
Both are thermally decomposed under reduced pressure at a high temperature of 100 ° C or higher,
N-vinylcarboxylic acid amide is obtained. The N-vinylcarboxylic acid amide is usually recovered from the pyrolysis mixture by distillation to obtain a crude N-vinylcarboxylic acid amide having a purity of usually 80% by weight or more. The N-vinylcarboxylic acid amide to be stabilized in the present invention may be a crude product as described above or a purified product. That is, the stabilizer used in the present invention is added to the N-vinylcarboxylic acid amide before distillation and purification obtained from the thermal decomposition step in the process for producing the N-vinylcarboxylic acid amide, and in the presence of the stabilizer. By distilling, it is possible to stabilize the distillation process. Further, it can be added to the purified N-vinylcarboxylic acid amide and stored and transported in the state of the composition to enhance the stability at that time.
【００１２】本発明で添加する安定剤は、前記式（１）
で表されるα，β−不飽和カルボニル化合物である。か
かる化合物の具体的な例としてはクロトンアルデヒド、
２，４−ヘキサジエナール（ソルビンアルデヒド）、桂
皮アルデヒド、クロトン酸アルキルエステル、桂皮酸ア
ルキルエステル類、ベンジリデンアセトンなどが例示さ
れる。また、幾何異性体として、トランス体を桂皮アル
デヒド、シス体をアロ桂皮アルデヒドとして別々に命名
する場合もあるが、本願明細書においては上記の例示化
合物はシス体、トランス体の幾何異性体の両方を含める
ものとする。また、Ｎ−ビニルカルボン酸アミドに対す
る安定剤の使用量が多くてもその効果を減ずるものでは
ないが、実用的には通常０．０１〜５重量％、好ましく
は０．１〜３重量％の範囲である。この場合、式（１）
で表される化合物を複数種使用してもよいし、幾何異性
体の混合物を使用してもよい。更に、従来公知のＮ−ビ
ニルカルボン酸アミドの安定剤である置換フェノール
類、芳香族アミン類、ハイドロキノン類等と併用しても
よい。なお、式（１）で表される化合物に対応する有機
酸、無水有機酸類は、Ｎ−ビニルカルボン酸アミドの分
解を促進し、かつ、安定化効果が低い傾向があるので、
その使用は好ましくない。The stabilizer added in the present invention has the formula (1) above.
Is an α, β-unsaturated carbonyl compound. Specific examples of such compounds include crotonaldehyde,
2,4-hexadienal (sorbin aldehyde), cinnamic aldehyde, crotonic acid alkyl ester, cinnamic acid alkyl ester, benzylideneacetone and the like are exemplified. In addition, as the geometric isomers, the trans form may be named separately as cinnamic aldehyde and the cis form may be named as allocinnamic aldehyde, but in the present specification, the above exemplary compounds are both cis and trans geometric isomers. Shall be included. Further, even if a large amount of the stabilizer is used with respect to the N-vinylcarboxylic acid amide, its effect is not reduced, but practically, it is usually 0.01 to 5% by weight, preferably 0.1 to 3% by weight. It is a range. In this case, equation (1)
A plurality of compounds represented by may be used, or a mixture of geometrical isomers may be used. Further, it may be used in combination with conventionally known stabilizers of N-vinylcarboxylic acid amides such as substituted phenols, aromatic amines and hydroquinones. The organic acids and organic acids corresponding to the compound represented by the formula (1) tend to promote the decomposition of N-vinylcarboxylic acid amide and have a low stabilizing effect.
Its use is not preferred.
【００１３】以上のような特定化合物によりＮ−ビニル
カルボン酸アミドを安定化することができる理由は明確
ではないが、以下のようなことが考えられる。炭素−炭
素二重結合に隣接するカルボニル基を有するα，β−不
飽和カルボニル化合物においては、そのカルボニル基が
電子吸引性であるために、β位の二重結合炭素の電子密
度が低下しており、そこでの求核付加反応を起こしやす
い。このような反応は一般にマイケル付加反応と呼ばれ
ている。一方、Ｎ−ビニルカルボン酸アミドは置換基と
して電子供与性の強いアシルアミド基を持っており、そ
の共重合反応性比から予測されるアシルアミド基の電子
供与性は、エーテル基と同等かそれよりも強いものであ
る。実際、Ｎ−ビニルカルボン酸アミドはビニルエーテ
ル同様に、容易にカチオン重合する性質を有する。The reason why the N-vinylcarboxylic acid amide can be stabilized by the above specific compound is not clear, but the following may be considered. In the α, β-unsaturated carbonyl compound having a carbonyl group adjacent to the carbon-carbon double bond, the electron density of the carbonyl group causes the electron density of the double bond carbon at the β-position to decrease. Therefore, the nucleophilic addition reaction there is likely to occur. Such a reaction is generally called a Michael addition reaction. On the other hand, N-vinylcarboxylic acid amide has an acylamide group having a strong electron donating property as a substituent, and the electron donating property of the acylamide group predicted from its copolymerization reactivity ratio is equal to or higher than that of an ether group. It is a strong one. In fact, N-vinylcarboxylic acid amide has a property of easily cationically polymerizing like vinyl ether.
【００１４】このようなＮ−ビニルカルボン酸アミドを
熱重合させた場合、活性種はラジカルであると予測され
るが、置換基の強い電子供与性により、この成長ラジカ
ルは比較的、電子密度の高い状態にある。このような系
に電子密度の低い、活性化された２重結合を持つα，β
不飽和カルボニル化合物が共存している場合、成長ラジ
カルは選択的にそのような化合物に付加していきやす
い。特に、β位に置換基を持たない場合は、Ｎ−ビニル
カルボン酸アミドと反応後、更なるＮ−ビニルカルボン
酸アミドを付加することができ、成長反応が継続するも
のと考えられる。ところが、その後の成長反応が抑制さ
れれば熱重合が停止するが、α，β不飽和カルボニル化
合物の中でも、式（１）で表される化合物でβ位に適当
な置換基を有するものは、その立体障害的な効果により
成長反応の抑制に効果を示すものと考えられる。一方、
β位の置換基でも電子供与性のカルボキシアルキル基や
ピロリドン基である場合は、熱重合成長種の付加反応に
おける反応性が低いと考えられる。When such an N-vinylcarboxylic acid amide is thermally polymerized, the active species are expected to be radicals, but this grown radical has a relatively high electron density due to the strong electron donating property of the substituent. It is in a high state. Α, β with activated double bonds with low electron density in such systems
When an unsaturated carbonyl compound coexists, the growing radical tends to selectively add to such a compound. In particular, when the β-position does not have a substituent, it is considered that after the reaction with N-vinylcarboxylic acid amide, further N-vinylcarboxylic acid amide can be added, and the growth reaction continues. However, if the subsequent growth reaction is suppressed, the thermal polymerization is stopped. Among the α, β unsaturated carbonyl compounds, the compound represented by the formula (1), which has an appropriate substituent at the β-position, is It is considered that the steric hindrance effect is effective in suppressing the growth reaction. on the other hand,
When the substituent at the β-position is also an electron-donating carboxyalkyl group or pyrrolidone group, it is considered that the reactivity in the addition reaction of the thermal polymerization growth species is low.
【００１５】以上のような式（１）で表されるα，β−
不飽和カルボニル化合物を添加して安定化させたＮ−ビ
ニルカルボン酸アミド組成物を精溜塔などを用いて蒸留
精製する場合、蒸留塔内での重合を抑制しつつ、収率よ
く高純度のＮ−ビニルカルボン酸アミドを安定に取得す
ることができる。塔の構造は一般的な蒸留塔の場合と同
様でよく、充填式、棚段式等が例示されうる。蒸留の操
作条件には特に制限はないが、工業的に実施しやすい条
件、すなわち、精溜塔の塔頂圧力が０．１〜３ＫＰａ、
対応する塔頂温度の範囲が５０〜１００℃程度において
も、熱重合物による精溜塔の閉塞を回避しうる。Α, β-represented by the above equation (1)
When an N-vinylcarboxylic acid amide composition that is stabilized by adding an unsaturated carbonyl compound is purified by distillation using a rectifying column or the like, while suppressing polymerization in the distillation column, a high yield and high purity are obtained. It is possible to stably obtain N-vinylcarboxylic acid amide. The structure of the column may be the same as that of a general distillation column, and examples thereof include a packing type and a tray type. The operating conditions for distillation are not particularly limited, but industrially easy to carry out, that is, the top pressure of the rectification column is 0.1 to 3 KPa,
Even when the corresponding column top temperature range is about 50 to 100 ° C., it is possible to avoid clogging of the rectification column due to the thermal polymer.
【００１６】[0016]
【実施例】以下に実施例により本発明をさらに具体的に
説明するが、本発明はその要旨を越えない限り、以下の
実施例に限定されるものではない。なお、実施例におい
て「％」は、「重量％」を意味する。 実施例１〜６、比較例１〜６ Ｎ−（α−メトキシエチル）ホルムアミドの熱分解反応
液を、減圧下に薄膜蒸発器を用いて蒸留し、メタノール
等の軽沸不純物と高沸の分解物を除去してＮ−ビニルホ
ルムアミドを得た。液体クロマトグラフィーによりこの
Ｎ−ビニルホルムアミドの組成を分析したところ、Ｎ−
ビニルホルムアミド９０．５％、Ｎ−（α−メトキシエ
チル）ホルムアミド２．２％、Ｎ−ビニルホルムアミド
二量体０．４％、ホルムアミド３．１％、メタノール
３．８％であった。The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. In Examples, "%" means "% by weight". Examples 1 to 6 and Comparative Examples 1 to 6 N- (α-methoxyethyl) formamide thermal decomposition reaction solutions were distilled under reduced pressure using a thin film evaporator to decompose light boiling impurities such as methanol and high boiling point decomposition. The substance was removed to obtain N-vinylformamide. The composition of this N-vinylformamide was analyzed by liquid chromatography,
The content was 90.5% vinylformamide, 2.2% N- (α-methoxyethyl) formamide, 0.4% N-vinylformamide dimer, 3.1% formamide, and 3.8% methanol.
【００１７】上記のＮ−ビニルホルムアミドに、表−１
に示すビニル化合物を、Ｎ−ビニルホルムアミドに対し
て各々１重量％添加し、常圧、窒素下で１１０℃、４時
間加熱処理した。加熱処理液について不溶性ポリマーの
発生状況を目視観察した。また、加熱処理液を液体クロ
マトグラフィーにより分析し、加熱処理液の組成を求め
た。結果を表−１に示す。In addition to the above N-vinylformamide, Table 1
1% by weight of each of the vinyl compounds shown in 1 was added to N-vinylformamide, and the mixture was heated at 110 ° C. for 4 hours under normal pressure and nitrogen. The generation state of the insoluble polymer was visually observed in the heat treatment liquid. Further, the heat treatment liquid was analyzed by liquid chromatography to determine the composition of the heat treatment liquid. The results are shown in Table 1.
【００１８】[0018]
【表１】 [Table 1]
【００１９】表−１において、「ＮＶＦ」は「Ｎ−ビニ
ルホルムアミド」を示し、「二量体」は「Ｎ−ビニルホ
ルムアミドの二量体」を示し、「ポリマー」は「Ｎ−ビ
ニルホルムアミドの二量体より高分子量成分の総量」を
示す。また、不溶性ポリマーの発生状況として、比較例
１に示すように、Ｎ−ビニルホルムアミドに安定化剤を
添加しない場合は、加熱後に膨潤した不溶性ポリマーが
発生して全体が固化したが、Ｎ−ビニルホルムアミドに
本発明の添加物を加えた実施例１〜６では、いずれの場
合も不溶性ポリマーは全く発生せず、分子量の低い可溶
性のポリマーがわずかに発生するのみであった。更に、
比較例２〜６にＮ−ビニルホルムアミドに一置換ビニル
化合物を添加した場合を示したが、比較例２のメタクリ
ル酸メチルを用いた場合には加熱後に液の半分程度固化
した状況が観察され、その他比較例３〜６では比較例１
と同様に液全体が固化した。In Table 1, "NVF" means "N-vinylformamide", "dimer" means "dimer of N-vinylformamide", and "polymer" means "N-vinylformamide". The total amount of higher molecular weight components than dimers "is shown. In addition, as the generation state of the insoluble polymer, as shown in Comparative Example 1, when the stabilizer was not added to N-vinylformamide, swollen insoluble polymer was generated after heating and the whole solidified. In each of Examples 1 to 6 in which the additive of the present invention was added to formamide, no insoluble polymer was generated at all, and only a small amount of soluble polymer having a low molecular weight was generated. Furthermore,
In Comparative Examples 2 to 6, the case where a mono-substituted vinyl compound was added to N-vinylformamide was shown, but when methyl methacrylate of Comparative Example 2 was used, a situation in which about half of the liquid solidified after heating was observed, In Comparative Examples 3 to 6, Comparative Example 1
The whole liquid solidified similarly to.
【００２０】実施例７ Ｎ−ビニルホルムアミドの精溜を、長さ１ｍ、直径５ｃ
ｍの塔に規則充填体（住友スルーザーラボパッキン）を
充填した装置を用いて実施した。あらかじめ安定剤とし
て桂皮アルデヒドを１重量％加えた原料Ｎ−ビニルホル
ムアミドを、塔の中段に連続的に供給しながら蒸留し
た。塔頂から純度９９．５％のＮ−ビニルホルムアミド
を連続的に得た。２４時間の運転後、塔を開放して調べ
たが、不溶性ポリマーの発生は全く認められなかった。Example 7 A rectifier of N-vinylformamide having a length of 1 m and a diameter of 5 c
It was carried out using an apparatus in which the m column was filled with regular packing (Sumitomo Sruzer Lab packing). The raw material N-vinylformamide to which 1% by weight of cinnamic aldehyde was previously added as a stabilizer was distilled while continuously supplying it to the middle stage of the column. N-vinylformamide having a purity of 99.5% was continuously obtained from the top of the column. After the operation for 24 hours, the column was opened and examined, but no generation of insoluble polymer was observed.
【００２１】比較例６ Ｎ−ビニルホルムアミドの精溜を、長さ１ｍ、直径５ｃ
ｍの塔に規則充填体（住友スルーザーラボパッキン）を
充填した装置を用いて実施した。原料Ｎ−ビニルホルム
アミドを塔の中段に連続的に供給しながら蒸留した。塔
頂から純度９９．５％のＮ−ビニルホルムアミドを連続
的に得た。２４時間の運転後、塔を開放して調べると、
原料供給口付近に不溶性ポリマーの発生を認めた。COMPARATIVE EXAMPLE 6 A N-vinylformamide rectified fraction was prepared to have a length of 1 m and a diameter of 5 c.
It was carried out using an apparatus in which the m column was filled with regular packing (Sumitomo Sruzer Lab packing). The raw material N-vinylformamide was distilled while continuously supplying it to the middle stage of the column. N-vinylformamide having a purity of 99.5% was continuously obtained from the top of the column. After operating for 24 hours, open the tower and check,
Generation of an insoluble polymer was observed near the raw material supply port.
【００２２】実施例８ Ｎ−ビニルホルムアミドに１重量％の桂皮アルデヒドを
加え、窒素下、２５℃で１００日間保存した。その後、
該液に５重量倍量のアセトンを加えたが、析出物は全く
認められなかった。Example 8 1% by weight of cinnamic aldehyde was added to N-vinylformamide and stored under nitrogen at 25 ° C. for 100 days. afterwards,
Acetone was added to this solution in an amount of 5 times by weight, but no precipitate was observed.
【００２３】比較例７ Ｎ−ビニルホルムアミドを、窒素下、２５℃で１００日
間保存した。その後、サンプルに５倍量のアセトンを加
えたところ、析出物を認めた。この物質は、Ｎ−ビニル
ホルムアミドに対して０．１％存在しており、ＩＲスペ
クトルならびにＮＭＲスペクトルより、Ｎ−ビニルホル
ムアミドの重合体であると同定された。Comparative Example 7 N-vinylformamide was stored under nitrogen at 25 ° C. for 100 days. Then, when a 5-fold amount of acetone was added to the sample, a precipitate was observed. This substance was present in an amount of 0.1% with respect to N-vinylformamide, and was identified as a polymer of N-vinylformamide by IR spectrum and NMR spectrum.
【００２４】[0024]
【発明の効果】本発明によれば、Ｎ−ビニルカルボン酸
アミドの精製、貯蔵、移動時における安定性を高めるこ
とができ、高品質の製品を安定に製造し、保存すること
ができる。また、本発明で用いるＮ−ビニルカルボン酸
アミドの安定剤は、適度な蒸気圧を有し、毒性が低く、
着色も少ない点においても優れている。EFFECTS OF THE INVENTION According to the present invention, the stability of N-vinylcarboxylic acid amide during purification, storage and transfer can be enhanced, and a high quality product can be stably produced and stored. The stabilizer of N-vinylcarboxylic acid amide used in the present invention has an appropriate vapor pressure and low toxicity,
It is also excellent in that it is less colored.
Claims (9)
式（１）で表されるα，β−不飽和カルボニル化合物を
添加することを特徴とするＮ−ビニルカルボン酸アミド
の安定化方法。 【化１】 （式（１）において、Ｒ1は水素原子、アルキル基、ア
リール基又はアルコキシ基、Ｒ2はアルキル基、アルケ
ニル基又はアリール基、Ｒ3，Ｒ4は水素原子、アルキル
基、アルケニル基又はアリール基を表す。）1. A method for stabilizing N-vinylcarboxylic acid amide, which comprises adding an α, β-unsaturated carbonyl compound represented by the following formula (1) to N-vinylcarboxylic acid amide. Embedded image (In the formula (1), R 1 is a hydrogen atom, an alkyl group, an aryl group or an alkoxy group, R 2 is an alkyl group, an alkenyl group or an aryl group, and R 3 and R 4 are a hydrogen atom, an alkyl group, an alkenyl group or an aryl group. Represents a group.)
ボニル化合物を、Ｎ−ビニルカルボン酸アミドに対して
０．０１〜５重量％添加することを特徴とする請求項１
の安定化方法。2. An α, β-unsaturated carbonyl compound represented by the formula (1) is added in an amount of 0.01 to 5% by weight based on the N-vinylcarboxylic acid amide.
Stabilization method.
ボニル化合物が、クロトンアルデヒド、２，４−ヘキサ
ジエナール、桂皮アルデヒド、クロトン酸アルキルエス
テル、桂皮酸アルキルエステル類、ベンジリデンアセト
ンのいずれかであることを特徴とする請求項１又は２の
安定化方法。3. The α, β-unsaturated carbonyl compound represented by the formula (1) is crotonaldehyde, 2,4-hexadienal, cinnamic aldehyde, crotonic acid alkyl ester, cinnamic acid alkyl ester, benzylideneacetone. 3. The stabilizing method according to claim 1, wherein the stabilizing method is any one of the following.
ルホルムアミドであることを特徴とする請求項１ないし
３のいずれかの安定化方法。4. The stabilizing method according to claim 1, wherein the N-vinylcarboxylic acid amide is N-vinylformamide.
定化させたＮ−ビニルカルボン酸アミドを蒸留すること
を特徴とするＮ−ビニルカルボン酸アミドの精製方法。5. A method for purifying N-vinylcarboxylic acid amide, which comprises distilling the N-vinylcarboxylic acid amide stabilized by the method according to any one of claims 1 to 4.
式（１）で表されるα，β−不飽和カルボニル化合物を
含有することを特徴とするＮ−ビニルカルボン酸アミド
組成物。 【化２】 （式（１）において、Ｒ1は水素原子、アルキル基、ア
リール基又はアルコキシ基、Ｒ2はアルキル基、アルケ
ニル基又はアリール基、Ｒ3，Ｒ4は水素原子、アルキル
基、アルケニル基又はアリール基を表す。）6. An N-vinylcarboxylic acid amide composition comprising an N-vinylcarboxylic acid amide and an α, β-unsaturated carbonyl compound represented by the following formula (1). Embedded image (In the formula (1), R 1 is a hydrogen atom, an alkyl group, an aryl group or an alkoxy group, R 2 is an alkyl group, an alkenyl group or an aryl group, and R 3 and R 4 are a hydrogen atom, an alkyl group, an alkenyl group or an aryl group. Represents a group.)
ボニル化合物を、Ｎ−ビニルカルボン酸アミドに対して
０．０１〜５重量％含有することを特徴とする請求項６
の組成物。7. The α, β-unsaturated carbonyl compound represented by the formula (1) is contained in an amount of 0.01 to 5% by weight based on the N-vinylcarboxylic acid amide.
Composition.
ボニル化合物が、クロトンアルデヒド、２，４−ヘキサ
ジエナール、桂皮アルデヒド、クロトン酸アルキルエス
テル、桂皮酸アルキルエステル類、ベンジリデンアセト
ンのいずれかであることを特徴とする請求項６又は７の
組成物。8. The α, β-unsaturated carbonyl compound represented by the formula (1) is crotonaldehyde, 2,4-hexadienal, cinnamic aldehyde, crotonic acid alkyl ester, cinnamic acid alkyl ester, benzylideneacetone. The composition according to claim 6 or 7, which is any one of the following:
ルホルムアミドであることを特徴とする請求項６ないし
８の組成物。9. The composition according to claim 6, wherein the N-vinylcarboxylic acid amide is N-vinylformamide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05296596A JP3584601B2 (en) | 1996-03-11 | 1996-03-11 | Method for stabilizing N-vinylcarboxylic acid amide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05296596A JP3584601B2 (en) | 1996-03-11 | 1996-03-11 | Method for stabilizing N-vinylcarboxylic acid amide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09249627A true JPH09249627A (en) | 1997-09-22 |
| JP3584601B2 JP3584601B2 (en) | 2004-11-04 |
Family
ID=12929611
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP05296596A Expired - Lifetime JP3584601B2 (en) | 1996-03-11 | 1996-03-11 | Method for stabilizing N-vinylcarboxylic acid amide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3584601B2 (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61289068A (en) * | 1985-06-15 | 1986-12-19 | Mitsubishi Chem Ind Ltd | Method for stabilizing N-vinylformamide |
| JPS62190153A (en) * | 1986-02-05 | 1987-08-20 | バスフ アクチェン ゲゼルシャフト | Purification method of N-vinylformamide |
| JPS63264559A (en) * | 1987-04-20 | 1988-11-01 | Mitsubishi Kasei Corp | Storage method of N-vinylformamide |
| JPH02188560A (en) * | 1988-11-18 | 1990-07-24 | Air Prod And Chem Inc | Method for purifying and polymerizing n-vinylacetoamide |
| JPH04235146A (en) * | 1990-05-24 | 1992-08-24 | Air Prod And Chem Inc | Process for preparing n-vinylamide |
| JPH0641034A (en) * | 1992-06-03 | 1994-02-15 | Basf Ag | Method for stabilizing n-vinylformamide |
| JPH0748312A (en) * | 1993-05-17 | 1995-02-21 | Rohm & Haas Co | Method for reducing impurities in monomer aqueous solution |
| JPH0848657A (en) * | 1994-05-30 | 1996-02-20 | Mitsubishi Chem Corp | Method for stabilizing N-vinylamide |
-
1996
- 1996-03-11 JP JP05296596A patent/JP3584601B2/en not_active Expired - Lifetime
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61289068A (en) * | 1985-06-15 | 1986-12-19 | Mitsubishi Chem Ind Ltd | Method for stabilizing N-vinylformamide |
| JPS62190153A (en) * | 1986-02-05 | 1987-08-20 | バスフ アクチェン ゲゼルシャフト | Purification method of N-vinylformamide |
| JPS63264559A (en) * | 1987-04-20 | 1988-11-01 | Mitsubishi Kasei Corp | Storage method of N-vinylformamide |
| JPH02188560A (en) * | 1988-11-18 | 1990-07-24 | Air Prod And Chem Inc | Method for purifying and polymerizing n-vinylacetoamide |
| JPH04235146A (en) * | 1990-05-24 | 1992-08-24 | Air Prod And Chem Inc | Process for preparing n-vinylamide |
| JPH0641034A (en) * | 1992-06-03 | 1994-02-15 | Basf Ag | Method for stabilizing n-vinylformamide |
| JPH0748312A (en) * | 1993-05-17 | 1995-02-21 | Rohm & Haas Co | Method for reducing impurities in monomer aqueous solution |
| JPH0848657A (en) * | 1994-05-30 | 1996-02-20 | Mitsubishi Chem Corp | Method for stabilizing N-vinylamide |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3584601B2 (en) | 2004-11-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5759358A (en) | Process for pure grade acrylic acid | |
| JP3682092B2 (en) | Method for producing pure grade acrylic acid | |
| CN102325800B (en) | Polymerization inhibitor compositions and methods of inhibiting polymerization of distillable monomers | |
| JP2014508713A (en) | Synthesis of methylene malonate substantially free of impurities | |
| JPH0751604B2 (en) | Composition for suppressing addition polymerization of acrylic acid and its ester | |
| TWI328571B (en) | Process for continuously preparing alkylamino(meth)-acrylamides | |
| EP0250325A2 (en) | Process for the preparation of aqueous solutions of unsaturated quaternary ammonium salts | |
| CA2061875C (en) | Purification of 6-aminocapronitrile | |
| CN1134408C (en) | Stabilization against unwanted free-radical polymerization of (meth) acrylates | |
| TWI680964B (en) | The use of stable lipophilic hydroxylamine compounds for inhibiting polymerization of vinyl monomers | |
| JP2992389B2 (en) | Racemization method for optically active 1-aryl-alkylamines | |
| CN107540545B (en) | Improved method for producing methylenemalonate | |
| EP1232138A1 (en) | Method for purifying (meth)acrylic monomers by distillation | |
| JPH09249627A (en) | Method for stabilizing N-vinylcarboxylic acid amide | |
| TW200848391A (en) | Process for the manufacture of substituted 2-cyano cinnamic esters | |
| JPS5826849A (en) | Manufacture of methacryl- and acrylamide | |
| JP7250426B2 (en) | Method for synthesizing and producing alkenyl compound | |
| JP3711627B2 (en) | Method for stabilizing N-vinylcarboxylic acid amide | |
| JP3584611B2 (en) | Method for preserving and purifying N-vinylcarboxylic acid amide | |
| JP3402499B2 (en) | Method for producing cyano norbornene | |
| JP2009179610A (en) | Composition containing methylene lactone compound and its stabilization method | |
| JP2017043543A (en) | Separation method of 4-hydroxystyrene compound | |
| JP6844106B2 (en) | Distillation method of unsaturated carboxylic acid silyl ester | |
| CN101035757B (en) | Stabilizers for use in NVP synthesis | |
| JPH0952861A (en) | Method for preventing polymerization of (meth) acrylic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20040413 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20040420 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20040616 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20040713 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20040726 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080813 Year of fee payment: 4 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080813 Year of fee payment: 4 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090813 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100813 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100813 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110813 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120813 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130813 Year of fee payment: 9 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313111 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130813 Year of fee payment: 9 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| EXPY | Cancellation because of completion of term |